Search

In recent years, due to modern techniques for the distribution, transport, and retail sale of food, the production of large amounts of non-biodegradable and bioaccumulative packaging waste has become a major environmental issue. To address this issue, new food packaging materials based on renewable biomass have been studied as eco-friendly, biodegradable, and biocompatible alternatives to synthetic materials. However, although these materials are not petrochemical derivatives, the presence of contaminants cannot be excluded. This work aims to extend the knowledge on bio-based packaging materials, researching the presence of contaminants potentially able to migrate to food at concentrations of concern. In this study, we focus on two classes of contaminants, organophosphate esters (OPEs) and perfluoroalkyl substances (PFASs), carrying out migration tests toward different simulants, according to the current European regulation. PFAS analysis was performed using high-resolution liquid chromatography coupled to ion trap-tandem mass spectrometry (QTrap). OPE analyses were performed both by gas chromatography–mass spectrometry (GC-MS) and high-resolution liquid chromatography coupled to triple quadrupole mass spectrometry (TQMS). Preliminary findings demonstrate the release of toxic OPEs and PFASs from bio-based food packaging, highlighting the need to investigate the presence of potentially harmful chemicals in these materials.

Poly- and perfluorinated alkyl substances (PFASs) are widely used in the electrical and electronic appliance industry to the point that waste of electrical and electronic equipment (WEEE), also known as e-waste, creates significant potential for PFAS exposure (by inhalation, ingestion, or dermal exposure) for people handling and recycling e-waste. The aim of this work was the development of an untargeted analytical approach in order to detect the presence of possible unknown PFASs in particulate matter collected in three Italian e-waste facilities through liquid chromatography coupled to high-resolution tandem mass spectrometry (LC-HR-MS/MS) in negative ionization mode. By means of three acquisition experiments, nine compounds were detected as candidate PFASs, and three were definitively confirmed by comparison with their authentic standards. Among these, bistriflimide (bis (trifluoromethylsulfonyl) imide), an ionic liquid with several promising technological applications, was the most abundant compound detected in all three recycling plants. This is the first study associating the presence of fluorinated ionic liquids with e-waste, and as these chemicals are not only toxic and persistent but also highly mobile, our results indicate the need to include them in future PFAS research. Only further data on their actual environmental diffusion will determine whether they are emerging pollutants or not.

The waste of electrical and electronic equipment (WEEE) is generally considered a secondary raw material for the recovery of valuable components. However, emerging issues regarding the impact of suspended particles arising from WEEE recycling operations are a concern. It was recently demonstrated that samples from three different WEEE plants were rich in organophosphate flame retardants (OPFRs). Since exposure to a xenobiotic can lead to its biotransformation through human metabolism routes, in the present study, the metabolism of eight OPFRs of interest in our sampling campaign (triphenyl phosphate (TPhP), tri-m-tolyl phosphate (TMTP), ethylhexyl diphenyl phosphate (EHDPhP), tributoxyethyl phosphate (TBOEP), diphenyl phosphate (DPhP), trichloroethyl phosphate (TCEP), tris(1,3-dichloropropan-2-yl) phosphate (TDClPP) and bisphenol A bis(diphenyl phosphate) (BDP)) was investigated. Their metabolism was studied at different time points in three matrices: human liver microsomes, human hepatocytes and human skin microsomes. This study, which was run using a common experimental setting, allowed easy comparison of results for each OPFR of interest, and a comparison with other data in the literature was performed. In particular, a number of metabolites not previously described were detected, and for the first time, it was shown that TPhP could be metabolized in human skin microsomes.

Fosetyl-aluminum is a synthetic fungicide administered to plants especially to prevent diseases caused by the members of the Peronosporales and several Phytophthora species. Herein, we present a selective liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to analyze residues of fosetyl-A1 in air particulate matter. This study was performed in perspective of an exposure assessment of this substance of health concern in environments where high levels of fosetly-Al, relatively to airborne particulate matter, can be found after spraying it. The cleanup procedure of the analyte, from sampled filters of atmospheric particulate matter, was optimized using a Strata X solid-phase extraction cartridge, after accelerated extraction by using water. The chromatographic separation was achieved using a polymeric column based on hydrophilic interaction in step elution with water/acetonitrile, whereas the mass spectrometric detection was performed in negative electrospray ionization. The proposed method resulted to be a simple, fast, and suitable method for confirmation purposes.

Speciation studies are based on fundamental models that relate the properties of biomimetic coordination compounds to the stability of the complexes. In addition to the classic approach based on solution studies, solid state properties have been recently proposed as supporting tools to understand the bioavailability of the involved metal. A ten-year long systematic study of several different complexes of imidazole substituted ligands with transition metal ions led our group to the definition of a model based on experimental evidences. This model revealed to be a useful tool to predict the stability of such coordination complexes and is based on the induced behavior under thermal stress. Several different solid state complexes were characterized by Thermally Induced Evolved Gas Analysis by Mass Spectrometry (TI-EGA-MS). This hyphenated technique provides fundamental information to determine the solid state properties and to create a model that relates stability to coordination. In this research, the model resulting from our ten-year long systematic study of complexes of transition metal ions with imidazole substituted ligands is described. In view of a systematic addition of information, new complexes of Cu(II), Zn(II), or Cd(II) with 2-propyl-4,5-imidazoledicarboxylic acid were precipitated, characterized, and studied by means of Thermally Induced Evolved Gas Analysis performed by mass spectrometry (TI-EGA-MS). The hyphenated approach was applied to enrich the information related to thermally induced steps, to confirm the supposed decomposition mechanism, and to determine the thermal stability of the studied complexes. Results, again, allowed supporting the theory that only two main characteristic and common thermally induced decomposition behaviors join the imidazole substituted complexes studied by our group. These two behaviors could be considered as typical trends and the model allowed to predict coordination behavior and to provide speciation information.

Mycotoxins exposure by inhalation and/or dermal contact is possible in different branches of industry especially where heavily dusty settings are present and the handling of dusty commodities is performed. This study aims to explore the validity of the biomonitoring as a tool to investigate the intake of mycotoxins in a population of workers operating in an Italian feed plant. Serum samples were collected for the determination of aflatoxins B1 (AFB1), AFB1-Lysine adduct and ochratoxin A (OTA). A method based on liquid−liquid extraction coupled with high resolution mass spectrometry determination was developed and fully validated. For AFB1, a high number of non-detected samples (90%) was found and no statistical difference was observed comparing workers and control group. None of the analyzed samples showed the presence of AFB1-Lysine adduct. For OTA, the 100% of the analyzed samples was positive with a 33% of the samples showing a concentration higher than the limit of quantification (LOQ), but no statistical difference was highlighted between the average levels of exposed and control groups. In conclusion, the presence of AFB1 and OTA in serum cannot be attributable to occupational exposure.